Multilayer thin film heterostrutuctures comprised of alternating layers of a poly (phenylene vinylene) (PPV) precursor and various polyanions were fabricated using a new self-assembly technique. Thermal treatment of these films produced multilayers of the fully conjugated form of PPV. Alternating Multilayers fabricated with inert polyanions such as sulfonated polystyrene exhibited a very strong photoluminescence whereas alternating multilayers fabricated with electron acceptor polyanions such as sulfonated C?O and poly (thiophene acetic acid) displayed a highly quenched luminescence. This latter behavior suggests that self-assembled Multilayers can be used to examine photoinduced charge transfer interactions between PPV and various electron acceptors.